JP2020079422A - Diluent for production of butyl rubber - Google Patents

Abstract

To provide methods to efficiently produce butyl rubber via a slurry polymerization process.SOLUTION: The process comprises providing at least two monomers, wherein at least one monomer is an isoolefin and at least one monomer is a multiolefin. The monomers are combined with an initiator and an organic diluent comprising 40-60 vol.% of methyl chloride and 40-60 vol.% of 1,1,1, 2-tetrafluoroethane and polymerized.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an effective method for producing butyl rubber by a slurry method in a novel diluent.

  Rubbers, especially those containing repeating units derived from isoolefins, are industrially produced by the carbocationic polymerization method. Of particular interest are elastomers of isobutylene and smaller amounts of multiolefins, such as isoprene.

  Carbocationic polymerization of isoolefins and their elastomericization with multiolefins is mechanistically complex. The catalyst system typically comprises two components: an initiator and a Lewis acid, such as aluminum trichloride, which is frequently used in large scale commercial processes.

  Examples of initiators include proton sources such as hydrogen halides, carboxylic acids, and water.

  During the initiation process, the isoolefin reacts with the Lewis acid and the initiator to produce carbenium ions, which in turn reacts with further monomers to produce new carbenium ions in the so-called growth stage. ..

  The type of monomer, polymerization temperature, and the particular combination of Lewis acid and initiator affect the growth chemistry, and thus the incorporation of the monomer into the growing polymer chain.

  In addition, the type of diluent or solvent and its polarity have been found to have a significant effect on the polymerization and final polymer product.

  The industry has generally accepted the widespread use of slurry polymerization processes for the production of butyl rubber, polyisobutylene, etc. in methyl chloride as a diluent. Typically, the polymerization process is carried out at low temperatures, generally below -90°C. Methyl chloride is used for a variety of reasons, including dissolving the monomer and aluminum chloride catalyst but not the polymer product. Methyl chloride also has a suitable freezing point and boiling point to allow low temperature polymerization and effective separation from the polymer and unreacted monomer. Slurry polymerization in methyl chloride is characterized in that a polymer concentration of up to 40 wt% is achieved in the reaction mixture, as opposed to a polymer concentration of typically up to 20 wt% in solution polymerization. Brings numerous benefits at. An acceptable relatively low viscosity polymerized mass is obtained, allowing the heat of polymerization to be removed more effectively by surface heat exchange. The slurry polymerization method in methyl chloride is used to produce high molecular weight polyisobutylene and isobutylene-isoprene butyl rubber polymers.

  From EP1572766A it is known to use hydrofluorocarbons as diluents for the preparation of copolymers of isoolefins, preferably isobutylene, and multiolefins, preferably conjugated dienes, more preferably isoprene.

EP1572766A U.S. Pat.No. 4,946,899 WO 2011/000922 A WO 2012/089823 A

the Encyclopedia of Chemical Technology, Kirk Othmer, 4th Edition, pp. 8-311

  However, at the low temperatures applied, the polymerization rate is typically low, and it is desirable to provide a method that allows higher throughput as compared to prior art methods.

According to one aspect of the invention, there is provided a method of making an elastomer, the method comprising at least the following steps:
a) providing a reaction medium comprising an organic diluent and at least two monomers wherein at least one monomer is an isoolefin and at least one monomer is a multiolefin;
b) polymerizing the monomers in the reaction medium in the presence of an initiator system to produce an organic medium containing the copolymer, the organic diluent, and any residual monomers,
Where the diluent is
40 to 60% by volume of methyl chloride, and 40 to 60% by volume of 1,1,1,2-tetrafluoroethane, the two components being 90 to 100% by volume of the total volume of diluent, Preferably it comprises 95 to 100% by volume, more preferably 98 to 100% by volume, even more preferably 99 to 100% by volume.

FIG. 6 shows the conversion and reaction Delta T for Examples 1-5. FIG. 6 shows the conversion and reaction Delta T for Examples 1-5. FIG. 1 is a diagram showing the molecular weight and polydispersity of Examples 1 to 5.

  The invention also includes the preferred embodiments, ranges, parameters all disclosed herein in combination with each other, or with the broadest range or parameter disclosed.

(monomer)
In this embodiment, in step a) there is provided a reaction medium comprising an organic diluent and at least two monomers, wherein at least one monomer is an isoolefin and at least one monomer is a multiolefin. is there.

  The term isoolefin, as used herein, refers to a compound containing one carbon-carbon double bond, wherein one carbon atom of the double bond is substituted with two alkyl groups and the other The carbon atoms of are substituted with two hydrogen atoms or one hydrogen atom and one alkyl group.

Examples of suitable isoolefins include isoolefin monomers having 4 to 16 carbon atoms, preferably 4 to 7 carbon atoms, such as isobutene, 2-methyl-1-butene, 3-methyl-1-. Includes butene and 2-methyl-2-butene. The preferred isoolefin is isobutene.
As used herein, the term multiolefin means a compound, which may be conjugated or non-conjugated, containing one or more carbon-carbon double bonds.

Examples of suitable multiolefins include isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperine, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2 -Methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 4-butyl-1,3-pentadiene, 2,3-dimethyl-1,3 -Pentadiene, 2,3-dibutyl 1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene , Cyclohexadiene, and 1-vinylcyclohexadiene.
Preferred multiolefins are isoprene and butadiene. Isoprene is particularly preferred.

The elastomer may further comprise another olefin that is neither an isoolefin nor a multiolefin.
Examples of such suitable olefins include β-pinene, styrene, divinylbenzene, diisopropenylbenzene, o-, m-, and p-alkylstyrenes such as o-, m-, and p-methylstyrene. Is included.

  In one embodiment, the monomers used in step a) are 80% by weight to 99.5% by weight, preferably 85% by weight to 98.0% by weight, preferably 85% by weight, based on the total weight of all the monomers used. To 96.5% by mass, even more preferably 85% to 95.0% by mass, at least one isoolefin monomer, and 0.5% to 20% by mass, preferably 2.0% to 15% by mass, more preferably 3.5% by mass. % To 15% by weight, and even more preferably 5.0% to 15% by weight, of at least one multiolefin monomer.

  In another embodiment, the monomer mixture comprises at least one isoolefin monomer in the range of 90% to 95% by weight, and 5% to 10% by weight, based on the total weight of all monomers used. Includes a range of multi-olefin monomers. Even more preferably, the monomer mixture comprises at least one isoolefin monomer in the range of 92% to 94% by weight, and 6% to 8% by weight, based on the total weight of all monomers used. Includes at least one multi-olefin monomer in the range. The isoolefin is preferably isobutene and the multiolefin is preferably isoprene.

  The multiolefin content of the elastomers produced according to the invention is typically 0.1 mol% or more, preferably 0.1 mol% to 15 mol%, in another embodiment 0.5 mol% or more, preferably 0.5 mol% to 10 mol%. %, in another embodiment 0.7 mol% or more, preferably 0.7 to 8.5 mol%, especially when isobutene and isoprene are used, especially 0.8 to 1.5 mol% or 1.5 to 2.5 mol%, or 2.5 to 4.5 mol %. %, or 4.5 to 8.5 mol %.

  Monomers are present in the reaction medium in an amount of 0.01 wt% to 80 wt%, preferably 0.1 wt% to 65 wt%, more preferably 10.0 wt% to 65.0 wt%, even more preferably 25.0 wt% to 65.0 wt%. May exist

  In one embodiment, the monomer is purified prior to use in step a), especially if recycled from step c). Purification of the monomers can be carried out by passing through an adsorption column containing a suitable molecular sieve or alumina-based adsorption material. To minimize interference with the polymerization reaction, the total concentration of water- and alcohol- and other organic oxygenates such as organic oxygenates is preferably reduced to less than about 10 ppm by weight.

(Diluent)
In one embodiment, the diluent is
42-58% by volume of methyl chloride, and 42-58% by volume of 1,1,1,2-tetrafluoroethane, the two components totaling 90 to 100% by volume of the total diluent. , Preferably 95 to 100% by volume, more preferably 98 to 100% by volume, even more preferably 99 to 100% by volume.

In another embodiment, the diluent is
45-55% by volume of methyl chloride and 45-55% by volume of 1,1,1,2-tetrafluoroethane, said two components being in total 90-100% by volume of the total diluent , Preferably 95 to 100% by volume, more preferably 98 to 100% by volume, even more preferably 99 to 100% by volume.

In yet another embodiment, the diluent is
48-52% by volume methyl chloride, and 48-52% by volume 1,1,1,2-tetrafluoroethane, said two components being in total 96 to 100% by volume of the total diluent %, preferably 98 to 100% by volume, more preferably 99 to 100% by volume, even more preferably 99.5 to 100% by volume.

When the balance up to 100% by volume is present, it is a diluent other than methyl chloride and 1,1,1,2-tetrafluoroethane, such as other fluorinated or chlorinated hydrocarbons or fluorinated and chlorinated It may include hydrocarbons or aliphatic hydrocarbons.
Examples of another chlorinated hydrocarbon include methylene chloride or ethyl chloride.

Another example of a fluorinated hydrocarbon is the formula: C _x H _y F _z , where x is 1 to 40, or 1 to 30, or 1 to 20, or 1 to 10, or 1 to 6, or 2 to 20, or 3 to 10, or 3 to 6, most preferably 1 to 3 and y and z are integers), and at least one of 1, 1, 1, Diluents that are not 1,2-tetrafluoroethane are included.

  In one embodiment, the fluorinated hydrocarbon is a saturated hydrofluorocarbon such as fluoromethane; difluoromethane; trifluoromethane; fluoroethane; 1,1-difluoroethane; 1,2-difluoroethane; 1,1,1-trifluoroethane. 1,1,2-trifluoroethane; 1,1,2,2-tetrafluoroethane; 1,1,1,2,2-pentafluoroethane; 1-fluoropropane; 2-fluoropropane; 1,1 -Difluoropropane; 1,2-Difluoropropane; 1,3-Difluoropropane; 2,2-Difluoropropane; 1,1,1-Trifluoropropane; 1,1,2-Trifluoropropane; 1,1,3 -Trifluoropropane; 1,2,2-trifluoropropane; 1,2,3-trifluoropropane; 1,1,1,2-tetrafluoropropane; 1,1,1,3-tetrafluoropropane; 1 1,1,2,2-Tetrafluoropropane; 1,1,2,3-Tetrafluoropropane; 1,1,3,3-Tetrafluoropropane; 1,2,2,3-Tetrafluoropropane; 1,1 1,1,2,2-Pentafluoropropane; 1,1,1,2,3-Pentafluoropropane; 1,1,1,3,3-Pentafluoropropane; 1,1,2,2,3-Penta Fluoropropane; 1,1,2,3,3-pentafluoropropane; 1,1,1,2,2,3-hexafluoropropane; 1,1,1,2,3,3-hexafluoropropane; 1 ,1,1,3,3,3-Hexafluoropropane; 1,1,1,2,2,3,3-heptafluoropropane; 1,1,1,2,3,3,3-heptafluoropropane 1-fluorobutane; 2-fluorobutane; 1,1-difluorobutane; 1,2-difluorobutane; 1,3-difluorobutane; 1,4-difluorobutane; 2,2-difluorobutane; 2,3- Difluorobutane; 1,1,1-Trifluorobutane; 1,1,2-Trifluorobutane; 1,1,3-Trifluorobutane; 1,1,4-Trifluorobutane; 1,2,2-Tri Fluorobutane; 1,2,3-Trifluorobutane; 1,3,3-Trifluorobutane; 2,2,3-Trifluorobutane; 1,1,1,2-Tetrafluorobutane; 1,1,1 1,3-Tetrafluorobutane; 1,1,1,4-Tetrafluorobutane; 1,1,2,2-Tetrafluorobutane; 1,1,2,3-Tetrafluorobutane Luorobutane; 1,1,2,4-Tetrafluorobutane; 1,1,3,3-Tetrafluorobutane; 1,1,3,4-Tetrafluorobutane; 1,1,4,4-Tetrafluorobutane; 1,2,2,3-tetrafluorobutane; 1,2,2,4-tetrafluorobutane; 1,2,3,3-tetrafluorobutane; 1,2,3,4-tetrafluorobutane; 2, 2,3,3-Tetrafluorobutane; 1,1,1,2,2-Pentafluorobutane; 1,1,1,2,3-Pentafluorobutane; 1,1,1,2,4-Pentafluoro Butane; 1,1,1,3,3-pentafluorobutane; 1,1,1,3,4-pentafluorobutane; 1,1,1,4,4-pentafluorobutane; 1,1,2, 2,3-pentafluorobutane; 1,1,2,2,4-pentafluorobutane; 1,1,2,3,3-pentafluorobutane; 1,1,2,4,4-pentafluorobutane; 1,1,3,3,4-pentafluorobutane; 1,2,2,3,3-pentafluorobutane; 1,2,2,3,4-pentafluorobutane; 1,1,1,2, 2,3-hexafluorobutane; 1,1,1,2,2,4-hexafluorobutane; 1,1,1,2,3,3-hexafluorobutane; 1,1,1,2,3, 4-hexafluorobutane; 1,1,1,2,4,4-hexafluorobutane; 1,1,1,3,3,4-hexafluorobutane; 1,1,1,3,4,4- Hexafluorobutane; 1,1,1,4,4,4-hexafluorobutane; 1,1,2,2,3,3-hexafluorobutane; 1,1,2,2,3,4-hexafluoro Butane; 1,1,2,2,4,4-hexafluorobutane; 1,1,2,3,3,4-hexafluorobutane; 1,1,2,3,4,4-hexafluorobutane; 1,2,2,3,3,4-hexafluorobutane; 1,1,1,2,2,3,3-heptafluorobutane; 1,1,1,2,2,4,4-heptafluoro Butane; 1,1,1,2,2,3,4-heptafluorobutane; 1,1,1,2,3,3,4-heptafluorobutane; 1,1,1,2,3,4, 4-heptafluorobutane; 1,1,1,2,4,4,4-heptafluorobutane; 1,1,1,3,3,4,4-heptafluorobutane; 1,1,1,2, 2,3,3,4-octafluorobutane; 1,1,1,2,2,3,4,4-octafluorobutane 1,1,1,2,3,3,4,4-octafluorobutane;1,1,1,2,2,4,4,4-octafluorobutane;1,1,1,2, 3,4,4,4-octafluorobutane; 1,1,1,2,2,3,3,4,4-nonafluorobutane; 1,1,1,2,2,3,4,4, 4-Nonafluorobutane; 1-Fluoro-2-methylpropane; 1,1-Difluoro-2-methylpropane; 1,3-Difluoro-2-methylpropane; 1,1,1-Trifluoro-2-methylpropane 1,1,3-trifluoro-2-methylpropane; 1,3-difluoro-2-(fluoromethyl)propane; 1,1,1,3-tetrafluoro-2-methylpropane; 1,1,3 1,3-Tetrafluoro-2-methylpropane; 1,1,3-Trifluoro-2-(fluoromethyl)propane; 1,1,1,3,3-Pentafluoro-2-methylpropane; 1,1, 3,3-Tetrafluoro-2-(fluoromethyl)propane; 1,1,1,3-Tetrafluoro-2-(fluoromethyl)propane; Fluorocyclobutane; 1,1-Difluorocyclobutane; 1,2-Difluorocyclobutane 1,3-difluorocyclobutane; 1,1,2-trifluorocyclobutane; 1,1,3-trifluorocyclobutane; 1,2,3-trifluorocyclobutane; 1,1,2,2-tetrafluorocyclobutane; 1,1,3,3-Tetrafluorocyclobutane; 1,1,2,2,3-Pentafluorocyclobutane; 1,1,2,3,3-Pentafluorocyclobutane; 1,1,2,2,3, 3-hexafluorocyclobutane; 1,1,2,2,3,4-hexafluorocyclobutane; 1,1,2,3,3,4-hexafluorocyclobutane; 1,1,2,2,3,3, It is selected from the group consisting of 4-heptafluorocyclobutane.

  Further examples of fluorinated hydrocarbons are vinyl fluoride; 1,2-difluoroethene; 1,1,2-trifluoroethene; 1-fluoropropene; 1,1-difluoropropene; 1,2-difluoropropene; 1,3-Difluoropropene; 2,3-Difluoropropene; 3,3-Difluoropropene; 1,1,2-Trifluoropropene; 1,1,3-Trifluoropropene; 1,2,3-Trifluoropropene 1,3,3-trifluoropropene; 2,3,3-trifluoropropene; 3,3,3-trifluoropropene; 1-fluoro-1-butene; 2-fluoro-1-butene; 3-fluoro -1-butene; 4-fluoro-1-butene; 1,1-difluoro-1-butene; 1,2-difluoro-1-butene; 1,3-difluoropropene; 1,4-difluoro-1-butene; 2,3-Difluoro-1-butene; 2,4-Difluoro-1-butene; 3,3-Difluoro-1-butene; 3,4-Difluoro-1-butene; 4,4-Difluoro-1-butene; 1,1,2-Trifluoro-1-butene; 1,1,3-Trifluoro-1-butene; 1,1,4-Trifluoro-1-butene; 1,2,3-Trifluoro-1- Butene; 1,2,4-trifluoro-1-butene; 1,3,3-trifluoro-1-butene; 1,3,4-trifluoro-1-butene; 1,4,4-trifluoro- 1-butene; 2,3,3-trifluoro-1-butene; 2,3,4-trifluoro-1-butene; 2,4,4-trifluoro-1-butene; 3,3,4-tri Fluoro-1-butene; 3,4,4-Trifluoro-1-butene; 4,4,4-Trifluoro-1-butene; 1,1,2,3-Tetrafluoro-1-butene; 1,1 1,2,4-Tetrafluoro-1-butene; 1,1,3,3-Tetrafluoro-1-butene; 1,1,3,4-Tetrafluoro-1-butene; 1,1,4,4- Tetrafluoro-1-butene; 1,2,3,3-Tetrafluoro-1-butene; 1,2,3,4-Tetrafluoro-1-butene; 1,2,4,4-Tetrafluoro-1- Butene; 1,3,3,4-tetrafluoro-1-butene; 1,3,4,4-tetrafluoro-1-butene; 1,4,4,4-tetrafluoro-1-butene; 2,3 2,3,4-Tetrafluoro-1-butene; 2,3,4,4-Tetrafluoro-1-butene; 2,4,4,4-Tetrafluoro-1- Butene; 3,3,4,4-tetrafluoro-1-butene; 3,4,4,4-tetrafluoro-1-butene; 1,1,2,3,3-pentafluoro-1-butene; 1 ,1,2,3,4-Pentafluoro-1-butene; 1,1,2,4,4-Pentafluoro-1-butene; 1,1,3,3,4-Pentafluoro-1-butene; 1,1,3,4,4-pentafluoro-1-butene; 1,1,4,4,4-pentafluoro-1-butene; 1,2,3,3,4-pentafluoro-1-butene 1,2,3,4,4-pentafluoro-1-butene; 1,2,4,4,4-pentafluoro-1-butene; 2,3,3,4,4-pentafluoro-1- Butene; 2,3,4,4,4-pentafluoro-1-butene; 3,3,4,4,4-pentafluoro-1-butene; 1,1,2,3,3,4-hexafluoro -1-butene; 1,1,2,3,4,4-hexafluoro-1-butene; 1,1,2,4,4,4-hexafluoro-1-butene; 1,2,3,3 ,4,4-Hexafluoro-1-butene; 1,2,3,4,4,4-hexafluoro-1-butene; 2,3,3,4,4,4-hexafluoro-1-butene; 1,1,2,3,3,4,4-heptafluoro-1-butene; 1,1,2,3,4,4,4-heptafluoro-1-butene; 1,1,3,3, 4,4,4-heptafluoro-1-butene; 1,2,3,3,4,4,4-heptafluoro-1-butene; 1-fluoro-2-butene; 2-fluoro-2-butene; 1,1-difluoro-2-butene; 1,2-difluoro-2-butene; 1,3-difluoro-2-butene; 1,4-difluoro-2-butene; 2,3-difluoro-2-butene; 1,1,1-Trifluoro-2-butene; 1,1,2-Trifluoro-2-butene; 1,1,3-Trifluoro-2-butene; 1,1,4-Trifluoro-2- Butene; 1,2,3-Trifluoro-2-butene; 1,2,4-Trifluoro-2-butene; 1,1,1,2-Tetrafluoro-2-butene; 1,1,1,3 -Tetrafluoro-2-butene; 1,1,1,4-Tetrafluoro-2-butene; 1,1,2,3-Tetrafluoro-2-butene; 1,1,2,4-Tetrafluoro-2 -Butene; 1,2,3,4-tetrafluoro-2-butene; 1,1,1,2,3-pentafluoro-2-butene; 1,1,1,2,4-pentafluoro-2- Butene; 1,1,1,3,4-pentafluoro-2-butene; 1,1,1,4,4-pentafluoro-2-butene; 1,1,2,3,4-pentafluoro-2 -Butene; 1,1,2,4,4-pentafluoro-2-butene; 1,1,1,2,3,4-hexafluoro-2-butene; 1,1,1,2,4,4 -Hexafluoro-2-butene; 1,1,1,3,4,4-hexafluoro-2-butene; 1,1,1,4,4,4-hexafluoro-2-butene; 1,1, 2,3,4,4-hexafluoro-2-butene; 1,1,1,2,3,4,4-heptafluoro-2-butene; 1,1,1,2,4,4,4- Heptafluoro-2-butene; and mixtures thereof.

Examples of aliphatic hydrocarbons are propane, isobutane, pentane, methylcyclopentane, isohexane, 2-methylpentane, 3-methylpentane, 2-methylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2 -Methylhexane, 3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2-methylheptane, 3-ethyl Hexane, 2,5-dimethylhexane, 2,2,4-trimethylpentane, octane, heptane, butane, ethane, methane, nonane, decane, dodecane, undecane, hexane, methylcyclohexane, cyclopropane, cyclobutane, cyclopentane, methyl Cyclopentane, 1,1-dimethylcyclopentane, cis-1,2-dimethylcyclopentane, trans-1,2-dimethylcyclopentane, trans-1,3-dimethylcyclopentane, ethylcyclopentane, cyclohexane, methylcyclohexane included.
The polymerization in step b) is typically carried out as a slurry polymerization.

(Initiator system)
In step b), the monomers in the reaction medium are polymerized in the presence of the initiator system to produce a medium containing the elastomer, the organic diluent and any residual monomers.

  Initiator systems, especially for elastomers obtained by cationic polymerization, typically comprise at least one Lewis acid and at least one initiator.

(Lewis acid)
Suitable Lewis acids include compounds of the formula MX _{3 where} M is a Group 13 element and X is a halogen. Examples of such compounds include aluminum trichloride, aluminum tribromide, boron trichloride, boron tribromide, gallium trichloride, and indium trifluoride, where aluminum trichloride is preferred.

Further suitable Lewis acids include the formula M _(m) X _{(3-m) where} M is a Group 13 element, X is halogen, R is C ₁ to C ₁₂ alkyl, C ₆ to A monovalent hydrocarbon group selected from the group consisting of C ₁₀ aryl, C ₇ to C ₁₄ arylalkyl, and C ₇ to C ₁₄ alkylaryl group; m is 1 or 2) Is included. X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide.

Examples of such compounds include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum. Includes chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, and mixtures thereof. Preferred are diethyl aluminum chloride (Et ₂ AlCl or DEAC), ethyl aluminum sesquichloride (Et _1.5 AlCl _1.5 or EAC), ethyl aluminum dichloride (EtAlCl ₂ or EADC), diethyl aluminum bromide (Et ₂ AlBr or DEAB), ethyl Aluminum sesquibromide (Et _1.5 AlBr _1.5 or EASB), and ethyl aluminum bromide (Et AlBr ₂ or EADB) and mixtures thereof.

Further suitable Lewis acids are of the formula M(RO) _n R′ _m X _(3-(m+n)) , where M is a Group 13 metal; RO is a C ₁ -C ₃₀ alkoxy, C ₇ aryloxy -C _30, C ₇ -C ₃₀ arylalkoxy, be hydrocarboxy monovalent group selected from the group consisting of alkyl aryloxy of C ₇ -C _30; R 'are as defined above C ₁ - A monovalent hydrocarbon group selected from the group consisting of C ₁₂ alkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ arylalkyl, and C ₇ -C ₁₄ alkylaryl groups; n is 0 to 3 Is a number, m is a number from 0 to 3, and the sum of n and m does not exceed 3).

  X is halogen, preferably chlorine, independently selected from the group consisting of fluorine, chlorine, bromine, and iodine. X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide.

  For the purposes of the present invention, those skilled in the art will recognize that alkoxy and aryloxy are the structural equivalents of alkoxides and phenoxides, respectively. The term "arylalkoxy" means a group containing both aliphatic and aromatic structures, where the radical is in the alkoxy position. The term "alkylaryl" means a group containing both aliphatic and aromatic structures, where the radical is in the aryloxy position.

  Non-limiting examples of these Lewis acids include methoxy aluminum dichloride, ethoxy aluminum dichloride, 2,6-di-tert-butylphenoxy aluminum dichloride, methoxymethyl aluminum chloride, 2,6-di-tert-butylphenoxymethyl. Includes aluminum chloride, isopropoxygallium dichloride, and phenoxymethylindium fluoride.

Further suitable Lewis acids have the formula _{M (RC = OO) n R} 'm X (3- (m + n)) ( wherein, M is an Group 13 metal; RC = OO is C ₁ -C ₃₀ be Alka sill oxy, C ₇ -C ₃₀ aryl acyloxyalkyl, C ₇ -C ₃₀ arylalkyl acyloxyalkyl, hydrocarbaryl sill monovalent group selected from the group consisting of alkylaryl acyl group of C ₇ -C ₃₀ R'is a monovalent hydrocarbon selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ arylalkyl, and C ₇ -C ₁₄ alkylaryl group as described above. A group; n is a number from 0 to 3, m is a number from 0 to 3, and the sum of n and m does not exceed 3; X is a group consisting of fluorine, chlorine, bromine, and iodine. More independently selected halogen, preferably chlorine). X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide.

  The term "arylalkylacyloxy" refers to a group containing both aliphatic and aromatic structures, where the radical is in the alkylacyloxy position. The term "alkylarylacyloxy" refers to a radical containing both aliphatic and aromatic structures, where the radical is in the arylacyloxy position. Non-limiting examples of these Lewis acids include acetoxy aluminum dichloride, benzoyloxy aluminum dibromide, benzoyloxy gallium difluoride, methyl acetoxy aluminum chloride, and isopropoyloxy indium trichloride.

  Further suitable Lewis acids include compounds based on metals of Groups 4, 5, 14, and 15 of the Periodic Table of the Elements, including titanium, zirconium, tin, vanadium, arsenic, antimony, and bismuth.

However, one of ordinary skill in the art will recognize that certain elements are more suitable for practicing the present invention. Groups 4, 5, and 14 Lewis acids are represented by the general formula MX ₄ (wherein M is a metal of Groups 4, 5, and 14; X is a group consisting of fluorine, chlorine, bromine, and iodine). More independently selected halogen, preferably chlorine, X may be azide, isocyanate, thiocyanate, isothiocyanate, or cyanide). Non-limiting examples include titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride, tin tetrachloride, and zirconium tetrachloride. The Group 4, 5, or 14 Lewis acid may include one or more types of halogens. Non-limiting examples include titanium trichloride bromide, titanium dichloride dibromide, vanadium trichloride bromide, and tin trifluoride chloride.

Groups 4, 5, and 14 Lewis acids useful in the present invention are represented by the general formula MR _n X _(4-n) , where M is a metal of Groups 4, 5, and 14; R is C A monovalent hydrocarbon group selected from the group consisting of ₁ to C ₁₂ alkyl, C ₆ to C ₁₀ aryl, C ₇ to C ₁₄ arylalkyl, and C ₇ to C ₁₄ alkylaryl groups; n is 0 to An integer of 4; X is a halogen independently selected from the group consisting of fluorine, chlorine, bromine, and iodine, preferably chlorine). X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide.

The term "arylalkyl" means a group containing both aliphatic and aromatic structures, where the radical is in the alkyl position.
The term "alkylaryl" means a group containing both aliphatic and aromatic structures, where the radical is in the aryl position.

  Non-limiting examples of Lewis acids include benzyl titanium trichloride, benzyl titanium dichloride, benzyl zirconium trichloride, dibenzyl zirconium dibromide, methyl titanium trichloride, dimethyl titanium difluoride, dimethyl tin dichloride, and Includes phenyl vanadium trichloride.

Lewis acids 4, 5, and Group 14 useful in the present invention have the general formula _{M (RO) n R 'm} X (4- (m + n)) ( wherein, M is 4, 5, and 14 Is a group metal; RO is selected from the group consisting of C ₁ -C ₃₀ alkoxy, C ₇ -C ₃₀ aryloxy, C ₇ -C ₃₀ arylalkoxy, C ₇ -C ₃₀ alkylaryloxy groups be hydrocarboxy monovalent radical; R 'is a monovalent hydrocarbon radical selected from the group consisting of, as R is the C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl, C ₇ - C ₁₄ arylalkyl, and a monovalent hydrocarbon group selected from the group consisting of C ₇ -C ₁₄ alkylaryl groups; n is an integer of 0 to 4, m is an integer of 0 to 4, The sum of n and m does not exceed 4; X is independently selected from the group consisting of fluorine, chlorine, bromine, and iodine, and is preferably chlorine. X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide.

  For the purposes of the present invention, those skilled in the art will recognize that alkoxy and aryloxy are the structural equivalents of alkoxides and phenoxides, respectively. The term "arylalkoxy" means a group containing both aliphatic and aromatic structures, where the radical is in the alkoxy position.

  The term "alkylaryl" means a group containing both aliphatic and aromatic structures, where the radical is in the aryloxy position. Non-limiting examples of these Lewis acids include methoxytitanium trichloride, n-butoxytitanium trichloride, di(isopropoxy)titanium dichloride, phenoxytitanium tribromide, phenylmethoxyzirconium trifluoride, methyl dichloride. Included are methoxytitanium, methyltin dichloride xoxytin, and benzylisopropoxy vanadium dichloride.

Lewis acids 4, 5, and Group 14 useful in the present invention is also in the general formula _{M (RC = OO) n R} 'm X 4- (m + n) ( wherein, M is 4, 5, and It is a group 14 metal; RC = OO is C ₁ -C ₃₀ alk sill oxy, C ₇ -C ₃₀ aryl acyloxyalkyl, C ₇ -C ₃₀ arylalkyl acyloxyalkyl, alkylaryl acyl group of C ₇ -C ₃₀ R′ is a C ₁ -C ₁₂ alkyl, a C ₆ -C ₁₀ aryl, a C ₇ -C ₁₄ arylalkyl, and a C ₇ -C _{14 as described above.} A monovalent hydrocarbon group selected from the group consisting of alkylaryl groups; n is an integer from 0 to 4, m is an integer from 0 to 4, and the sum of n and m does not exceed 4. X is a halogen independently selected from the group consisting of fluorine, chlorine, bromine, and iodine, preferably chlorine). X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide.

  The term "arylalkylacyloxy" refers to a group containing both aliphatic and aromatic structures, where the radical is in the alkylacyloxy position.

  The term "alkylarylacyloxy" refers to a radical containing both aliphatic and aromatic structures, where the radical is in the arylacyloxy position. Non-limiting examples of these Lewis acids include acetoxytitanium trichloride, benzoylzirconium tribromide, benzoyloxytitanium trifluoride, isopropoyloxytin trichloride, methylacetoxytitanium dichloride, and benzyl benzoyl oxyvanadium chloride. Is included.

Group 5 Lewis acids useful in the present invention also have the general formula MOX ₃ , where M is a Group 5 metal and X is independently selected from the group consisting of fluorine, chlorine, bromine, and iodine. Halogen, preferably chlorine). A non-limiting example is vanadium oxytrichloride. The Group 15 Lewis acid has the general formula MX _y , where M is a Group 15 metal and X is a halogen independently selected from the group consisting of fluorine, chlorine, bromine, and iodine, preferably chlorine. , Y is 3, 4, or 5). X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide. Non-limiting examples include antimony hexachloride, antimony hexafluoride, and arsenic pentafluoride. Group 15 Lewis acids may include one or more types of halogen. Non-limiting examples include antimony chloride pentafluoride, arsenic trifluoride, bismuth trichloride, and arsenic fluoride tetrachloride.

Group 15 Lewis acids useful in the present invention have the general formula MR _n X _yn , where M is a Group 15 element, R is C ₁ to C ₁₂ alkyl, C ₆ to C ₁₀ aryl, C ₇ To C ₁₄ arylalkyl, and a monovalent hydrocarbon group selected from the group consisting of C ₇ to C ₁₄ alkylaryl groups; n is an integer from 0 to 4; y is 3, 4, or 5; Yes; n is less than y; X is a halogen independently selected from the group consisting of fluorine, chlorine, bromine, and iodine, preferably chlorine). X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide. The term "arylalkyl" means a group containing both aliphatic and aromatic structures, where the radical is in the alkyl position. The term "alkylaryl" means a group containing both aliphatic and aromatic structures, where the radical is in the aryl position. Non-limiting examples of these Lewis acids include tetraphenyl antimony chloride and triphenyl antimony dichloride.

Group 15 Lewis acids useful in the present invention also have the general formula _{M (RO) n R 'm} X y- (m + n) ( wherein, M is an Group 15 metal; RO is C ₁ -C ₃₀ Is a monovalent hydrocarboxy group selected from the group consisting of alkoxy, C ₇ -C ₃₀ aryloxy, C ₇ -C ₃₀ arylalkoxy, and C ₇ -C ₃₀ alkylaryloxy group; R′ is A monovalent hydrocarbon group selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ arylalkyl, and C ₇ -C ₁₄ alkylaryl group as described above; n is an integer from 0 to 4, m is an integer from 0 to 4, y is 3, 4, or 5, and the sum of n and m does not exceed y; X is fluorine, chlorine, Independently selected from the group consisting of bromine and iodine, preferably chlorine). X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide. For purposes of the present invention, those skilled in the art will recognize that the terms alkoxy and aryloxy are structurally equivalent to alkoxide and phenoxide, respectively. The term "arylalkoxy" refers to a group containing both aliphatic and aromatic structures, where the radical is in the alkoxy position. The term "alkylaryl" means a group containing both aliphatic and aromatic structures, where the radical is in the aryloxy position. Non-limiting examples of these Lewis acids include tetrachloromethoxyantimony, dimethoxytrichloroantimony, dichloromethoxyarsine, chlorodimethoxyarsine, and difluoromethoxyarsine. Group 15 Lewis acids useful in the present invention have the general formula _{M (RC = OO) n R} 'm X y- (m + n) ( wherein, M is an Group 15 metal; RC = OO is C ₁ Arca sill oxy -C _30, C ₇ -C ₃₀ aryl acyloxyalkyl, C ₇ -C ₃₀ arylalkyl acyloxyalkyl, monovalent hydrocarbaryl sill selected from the group consisting of alkylaryl acyl group of C ₇ -C ₃₀ An oxy group; R'is one selected from the group consisting of C ₁ -C ₁₂ alkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ arylalkyl, and C ₇ -C ₁₄ alkylaryl group as described above. A valent hydrocarbon group; n is an integer from 0 to 4, m is an integer from 0 to 4, y is 3, 4, or 5, and the sum of n and m does not exceed y X is a halogen independently selected from the group consisting of fluorine, chlorine, bromine, and iodine, preferably chlorine). X may be an azide, an isocyanate, a thiocyanate, an isothiocyanate, or a cyanide. The term "arylalkylacyloxy" refers to a radical containing both aliphatic and aromatic structures, where the radical is in the alkylacyloxy position. The term "alkylarylacyloxy" refers to a group containing both aliphatic and aromatic structures, where the radical is in the arylacyloxy position. Non-limiting examples of these Lewis acids include acetotetrachloroantimony, (benzoato)tetrachloroantimony, and bismuth acetate chloride.

Lewis acids such as methylaluminoxane (MAO) and specially designed weakly coordinating Lewis acids such as B(C ₆ F ₅ ) ₃ are also suitable Lewis acids within the scope of the present invention.

  Weakly coordinating Lewis acids are exhaustively disclosed in paragraphs [117] to [129] of WO 2004/067577A, which is hereby incorporated by reference.

(Initiator)
Initiators useful in the present invention are initiators that can be complexed with a selected Lewis acid to give a complex that reacts with the monomer to form a growing polymer chain.

  In a preferred embodiment, the initiator is water, hydrogen halide, carboxylic acid, carboxylic acid halide, sulfonic acid, sulfonic acid halide, alcohol, phenol, tertiary alkyl halide, tertiary aralkyl halide, secondary At least selected from the group consisting of tertiary alkyl esters, tertiary aralkyl esters, tertiary alkyl ethers, tertiary aralkyl ethers, alkyl halides, aryl halides, alkylaryl halides, and arylalkyl acid halides Contains one compound.

  Preferred hydrogen halide initiators include hydrogen chloride, hydrogen bromide, and hydrogen iodide. A particularly preferred hydrogen halide is hydrogen chloride.

  Preferred carboxylic acids include both aliphatic and aromatic carboxylic acids. Examples of carboxylic acids useful in the present invention include acetic acid, propanoic acid, butanoic acid, cinnamic acid, benzoic acid, 1-chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, p-chlorobenzoic acid, and p- Fluorobenzoic acid is included. Particularly preferred carboxylic acids include trichloroacetic acid, trifluoroacetic acid, and p-fluorobenzoic acid.

  Carboxylic acid halides useful in the present invention are similar in structure to carboxylic acids, where the OH of the acid is replaced by a halide. The halide may be fluoride, chloride, bromide, or iodide, with chloride being preferred.

  Carboxylic acid halides useful in the present invention include acetyl chloride, acetyl bromide, cinnamyl chloride, benzoyl chloride, benzoyl bromide, trichloroacetyl chloride, trifluoroacetyl chloride, trifluoroacetyl chloride, and p-fluorobenzoyl chloride. included. Particularly preferred acid halides include acetyl chloride, acetyl bromide, trichloroacetyl chloride, trifluoroacetyl chloride, and p-fluorobenzoyl chloride.

  Sulfonic acids useful as initiators in the present invention include both aliphatic and aromatic sulfonic acids. Examples of preferred sulfonic acids include methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, and p-toluenesulfonic acid.

  Sulfonic acid halides useful in the present invention are similar in structure to sulfonic acids and are the OH of the parent acid replaced with a halide. The halide may be fluoride, chloride, bromide, or iodide, with chloride being preferred. The production of sulfonic acid halides from parent sulfonic acids is known in the prior art and the person skilled in the art should be familiar with these procedures. Preferred sulfonic acid halides useful in the present invention include methanesulfonyl chloride, methanesulfonyl bromide, trichloromethanesulfonyl chloride, trifluoromethanesulfonyl chloride, and p-toluenesulfonyl chloride.

  Alcohols useful in the present invention include methanol, ethanol, propanol, 2-propanol, 2-methylpropan-2-ol, cyclohexanol, and benzyl alcohol. Phenols useful in the present invention include phenol; 2-methylphenol; 2,6-dimethylphenol; p-chlorophenol; p-fluorophenol; 2,3,4,5,6-pentafluorophenol; and 2- Includes hydroxynaphthalene.

Preferred tertiary alkyl and aralkyl initiators include tertiary compounds represented by the formulas below, wherein X is halogen, pseudohalogen, ether, or ester, or a mixture thereof, preferably halogen, Preferably chloride, R ₁ , R ₂ and R ₃ are independently linear, cyclic, or branched, preferably containing from 1 to 15 carbon atoms, more preferably from 1 to 8 carbon atoms. It is a chain alkyl, aryl, or arylalkyl. n is the number of initiator moieties, is 1 or greater, preferably 1 to 30, and more preferably n is a number from 1 to 6. The arylalkyl may be substituted or unsubstituted. In the present invention and its claims, arylalkyl is defined to mean a compound containing both aromatic and aliphatic structures. Preferred examples of the initiator include 2-chloro-2,4,4-trimethylpentane; 2-bromo-2,4,4-trimethylpentane; 2-chloro-2-methylpropane; 2-bromo-2-methyl Propane; 2-chloro-2,4,4,6,6-pentamethylheptane; 2-bromo-2,4,4,6,6-pentamethylheptane; 1-chloro-1-methylethylbenzene; 1-chloro Adamantane; 1-chloroethylbenzene; 1,4-bis(1-chloro-1-methylethyl)benzene; 5-tert-butyl-1,3-bis(1-chloro-1-methylethyl)benzene; 2-acetoxy -2,4,4-Trimethylpentane; 2-benzoyloxy-2,4,4-trimethylpentane; 2-acetoxy-2-methylpropane; 2-benzoyloxy-2-methylpropane; 2-acetoxy-2,4 ,4,6,6-Pentamethylheptane; 2-benzoyl-2,4,4,6,6-pentamethylheptane; 1-acetoxy-1-methylethylbenzene; 1-acetoxyadamantane; 1-benzoyloxyethylbenzene; 1 ,4-Bis(1-acetoxy-1-methylethyl)benzene; 5-tert-butyl-1,3-bis(1-acetoxy-1-methylethyl)benzene; 2-methoxy-2,4,4-trimethyl Pentane; 2-isopropoxy-2,4,4-trimethylpentane; 2-methoxy-2-methylpropane; 2-benzyloxy-2-methylpropane; 2-methoxy-2,4,4,6,6-penta Methylheptane; 2-isopropoxy-2,4,4,6,6-pentamethylheptane; 1-methoxy-1-methylethylbenzene; 1-methoxyadamantane; 1-methoxyethylbenzene; 1,4-bis(1-methoxy) -1-Methylethyl)benzene; 5-tert-butyl-1,3-bis(1-methoxy-1-methylethyl)benzene, and 1,3,5-tris(1-chloro-1-methylethyl)benzene Is included. Other suitable initiators can be found in US Pat. No. 4,946,899. In the present invention and in its claims, pseudohalogen is defined as any compound which is an azide, isocyanate, thiocyanate, isothiocyanate or cyanide.

Another preferred initiator is a polymeric halide, one of R ₁ , R ₂ or R ₃ is an olefin polymer and the remaining R groups are as defined above. Preferred olefin polymers include polyisobutylene, polypropylene and polyvinyl chloride. The polymerization initiator may have a halogenated tertiary carbon located at the end of the polymer chain, along the backbone, or in the backbone. If the olefin polymer has multiple halogen atoms at the tertiary carbon, whether pendant to the polymer backbone or present within the backbone, the product will have a number of halogen atoms in the olefin polymer and its Depending on the position, it may include polymers with comb structures and/or side chain branches. Similarly, the use of chain-terminated tertiary halide initiators provides a method of making products that may contain block elastomers.

  Particularly preferred initiators may be anything useful in the cationic polymerization of isobutylene elastomers, such as water, hydrogen chloride, 2-chloro-2,4,4-trimethylpentane, 2-chloro-2-methylpropane, 1- Contains chloro-1-methylethylbenzene, and methanol.

  The initiator system useful in the present invention may further comprise a composition comprising a reactive cation and a weakly coordinating anion ("WCA") as defined above.

  The preferred molar ratio of Lewis acid to initiator is generally 1:5 to 100:1, preferably 5:1 to 100:1, more preferably 8:1 to 20:1.

  The Lewis acid is preferably present in the reaction mixture in an amount of 0.002 to 5.0 mol %, preferably 0.1 to 0.5 mol %, based on the total monomers.

  Of course, it is understood that higher or lower amounts of initiator are still within the scope of the invention.

  In a particularly preferred initiator system, the Lewis acid is ethyl aluminum sesquichloride, preferably produced by mixing equimolar amounts of diethyl aluminum chloride and ethyl aluminum dichloride, preferably in a diluent.

  In another particularly preferred initiator system, the Lewis acid is ethyl aluminum dichloride, preferably in the diluent.

  If an alkylaluminum halide is used, hydrogen chloride water and/or alcohol, preferably water, is used as the proton source.

  In one embodiment, the amount of water is in the range of 0.40 to 4.0 moles of water per mole of aluminum of the alkylaluminum halide, preferably 0.5 to 2.5 moles of water per mole of aluminum of the alkylaluminum halide. And most preferably, the range is 1 to 2 moles of water per mole of aluminum of the alkylaluminum halide.

  In another embodiment, the amount of hydrogen chloride is in the range of 0.10 to 1 mole of hydrogen chloride per mole of aluminum of the alkylaluminum halide, preferably hydrogen chloride per mole of aluminum of the alkylaluminum halide. It is in the range of 0.2 to 0.5 mol.

(Polymerization conditions)
In one embodiment, the organic diluent and monomer used are substantially free of water. Substantially free of water herein means less than 50 ppm, preferably less than 30 ppm, more preferably less than 20 ppm, even more preferably less than 10 ppm, still more preferably less than 5 ppm based on the total mass of the reaction medium. Is defined as

  Those skilled in the art will appreciate that organic diluents and monomers in organic diluents and monomers may be confident that the initiator system will not be affected by additional amounts of water that have not been added, for example, to act as initiators. We recognize that we need to lower the water content.

  Steps a) and/or b) may be carried out in a continuous or batch process, the continuous process being preferred.

  In an embodiment of the invention, the polymerization of step b) is carried out using a polymerization reactor. Suitable reactors are known to those skilled in the art and include flow-through polymerization reactors, plug flow reactors, stirred tank reactors, moving belt or drum reactors, jet or nozzle reactors, tubular reactors, and automatic reactors. Included are autorefrigerated boiling-pool reactors. Particularly preferred embodiments are disclosed in WO 2011/000922 A and WO 2012/089823 A.

  In one embodiment, the polymerization of step b) is carried out with the initiator system, the monomer and the organic diluent present in a single phase. Preferably, the polymerization is carried out by a continuous polymerization process in which the initiator system, the monomer and the organic diluent are present in a single phase.

  In slurry polymerization, all of the monomers, initiator system are typically soluble in the diluent or diluent mixture, i.e. constituting a single phase, while the elastomer is formed and organic diluent Settle. "Swelling of the polymer, as indicated by little or no Tg suppression of the polymer and/or little or no mass uptake of the organic diluent. )” is reduced or not shown at all.

  The solubility of the desired polymers in the organic diluents mentioned above, as well as the swelling behavior under these reaction conditions, are well known to the person skilled in the art.

  In one embodiment, step b) comprises in the range of 20°C from the freezing point of the diluent, typically in the range of -100°C to 20°C, preferably in the range of -100°C to -50°C, and even more preferably It is carried out at temperatures ranging from -95°C to -70°C.

  In a preferred embodiment, the polymerization temperature is in the range of 20°C above the freezing point of the organic diluent, preferably 10°C above the freezing point of the organic diluent.

The reaction pressure in step b) is typically 100 to 100,000 hPa, preferably 200 to 20,000 hPa, more preferably 500 to 5,000 hPa.
The polymerization according to step b) is typically such that the solids content of the slurry in step b) is preferably 1 to 45% by weight, more preferably 3 to 40% by weight, even more preferably 15 to 40% by weight. It is carried out in a ranged manner.

As used herein, the term "solids content" or "solids level" includes the elastomer obtained by step b), i.e. polymerization, obtained by step b), the organic diluent and any residual monomers. Mean% by weight of elastomer present in the reaction medium.
In one embodiment, the reaction time in step b) is 2 minutes to 2 hours, preferably 10 minutes to 1 hour, more preferably 20 to 45 minutes.

  The method may be carried out batchwise or continuously. When continuous reactions are carried out, the reaction times mentioned above represent the average residence time.

  In one embodiment, the reaction is quenched with a quenching agent, such as a 1 wt% sodium hydroxide solution in water, methanol, or ethanol.

  In another embodiment, the reaction is quenched by contacting with an aqueous medium in step c), which in one embodiment is 5 to 10, preferably 6 to 5, measured at 1013 hPa at 20°C. It may have a pH value of 9, more preferably 7 to 9.

  If desired, the pH may be adjusted, preferably by adding an acid or alkali compound free of polyvalent metal ions. The pH adjustment to higher pH values is achieved, for example, by adding sodium hydroxide or potassium hydroxide.

  The conversion is typically 5% to 90%, preferably 5 to 50%, and in another embodiment 5% to 25%, preferably 10 to 20% by weight of the initially used monomer. It is stopped after the consumption of% monomer.

  The elastomer may be isolated by standard techniques known to those skilled in the art.

  Typically, in step c) residual monomers of the monomer mixture, preferably further diluent, are at least partially removed from the reaction medium, preferably by distillation, to give an elastomer.

  Removal of residual monomer and diluent may use another type of distillation to remove the desired amount of residual monomer and organic diluent either sequentially or together. Distillation methods for separating liquids with different boiling points are well known to those of skill in the art and are, for example, the Encyclopedia of Chemical Technology, Kirk Othmer, 4th Edition, pp. 8 which is incorporated herein by reference. -311. Generally, the diluent and residual monomer, whether separate or together, may be reused in step a) of the polymerization reaction.

  In one embodiment, the weight average molecular weight of the elastomer obtained according to the present invention is in the range of 10 to 2,000 kg/mol, preferably in the range of 20 to 1.000 kg/mol, more preferably in the range of 50 to 1,000 kg/mol, and further More preferably in the range 200 to 800 kg/mol, even more preferably in the range 250 to 550 kg/mol, and most preferably in the range 250 to 500 kg/mol. Molecular weights were obtained using gel permeation chromatography in tetrahydrofuran (THF) solution with polystyrene molecular weight standards unless otherwise stated.

  In one embodiment, the polydispersity of the elastomer according to the invention is in the range 1.5 to 4.5, preferably 2.0 to 3.5, measured by the ratio of the weight average molecular weight to the number average molecular weight determined by gel permeation chromatography. .

  The elastomer has a Mooney viscosity of at least 30 (ML 1+8, 125° C., ASTM D 1646), preferably 30 to 60, more preferably 30 to 45 (ML 1+8, 125° C., ASTM D 1646).

  The present invention further includes elastomers obtainable by the method of the present invention.

  An advantage of the present invention is the fact that the novel diluent blends according to the invention can achieve very high reaction rates at low temperatures while at the same time obtaining elastomers with low polydispersity.

  The present invention is further described below by way of non-limiting examples.

Experiment:
(General operation for polymerization)
All polymerizations were carried out in a dry, inert atmosphere. The batch reaction was performed in a 600 mL stainless steel reaction vessel equipped with an overhead 4-blade stainless steel impeller driven by an external electric stirrer. The reaction temperature was measured by a thermocouple. The reactor was cooled to the desired reaction temperature listed in the table by immersing the assembled reactor in a pentane cooling bath. The temperature of the stirred hydrocarbon bath was controlled at ±2°C. All equipment in liquid contact with the reaction medium were dried at 150° C. for at least 6 hours and cooled in a vacuum-nitrogen atmosphere alternating chamber before use.

High-purity isobutene and methyl chloride were received from the production facility and used as they were. Hydrofluorocarbon 1,1,1,2-tetrafluoroethane (purity >99.9%) (HFC-134a, Genetron@ 134a) was used as received. All was condensed and collected as a liquid in the dry box.
Isoprene (Sigma-Aldrich, >99.5% pure) was dried over activated 3A molecular sieves for several days and distilled under nitrogen. A 1.0 M solution of ethyl aluminum dichloride in hexane (Sigma-Aldrich) was used as received.
A solution of HCl/CH ₂ Cl ₂ is bubbled with anhydrous HCl gas (Sigma-Aldrich, 99% purity) into a pre-dried Sure/Steal® bottle containing anhydrous CH ₂ Cl ₂ (VWR). It was prepared by The HCl/CH ₂ Cl ₂ solution was then titrated with 0.1 N NaOH (VWR) standard solution to determine its concentration.

  Slurry polymerization was carried out by charging a cooled 600 mL stainless steel reaction vessel with isobutene, isoprene, and diluent (specified in each example) at the polymerization temperature, at a specified stirring speed of 500 to 900 rpm. It was stirred.

The initiator system was prepared in methyl chloride. The initiator system was prepared by diluting an HCl/CH ₂ Cl ₂ solution into an aliquot of methyl chloride and adding a 1.0 M solution of ethyl aluminum dichloride to a 1:4 molar ratio of HCl:EADC followed by gentle stirring. , Was prepared under the same conditions as the reaction container. The initiator/co-initiator solution was used immediately and added to the polymerization using a chilled glass Pasteur pipette. The reaction was allowed to proceed for 5 minutes and stopped by the addition of 2 mL of 1% sodium hydroxide in ethanol solution. Conversion is reported as the weight percent of monomer converted to polymer during polymerization after polymer isolation and vacuum drying.

(Raman spectroscopy)
Kaiser Raman RXN2 was used to take spectra from 0 to 3400 cm ⁻¹ with Kaiser Optical Systems iC Raman or lower software, version 4.1.915 SP1, using the following parameters: laser wavelength 785 nm, resampling interval. : 1 cm ^-1 , automatic adjustment enabled, frequency: 1 day; channel 1; automatic exposure adjustment enabled, total target exposure time: 6 seconds, cosmic ray removal: true, intensity correction: true. Spectra were collected at scan exposure times ranging from 0.8 seconds to 2.0 seconds at 10 or 11 second intervals, for a total of 4 scan results. Spectra of diluent and isoprene alone were collected prior to the addition of isobutene to obtain a baseline in the absence of isobutene. After the addition of isobutene and the initiator, the reaction was observed utilizing the isobutene peak from 800 to 815 cm ^-1 . Peak areas were calculated from a 2-point baseline selection around each peak.

(Characteristic evaluation): Incorporation of isoprene (total degree of unsaturation) was measured by ¹ H-NMR spectrum. NMR measurements were performed with a Bruker DRX 500 MHz spectrometer (500.13 MHz) using a solution of the polymer with the residual CHCl ₃ peak in CDCl ₃ used as an internal standard.

  Polymer molecular weights were measured by GPC (gel permeation chromatography) using a Waters 2690/5 Separations Module and a Waters 2414 refractive index detector. Tetrahydrofuran was used as the eluent (0.8 mL/min, 35° C.) with a series of three Agilent PL gel 10 μm Mixes-B LS300×5.7 mm columns.

(Examples 1 to 5)
A series of polymerizations was performed in pure methyl chloride, pure 1,1,1,2-tetrafluoroethane, and various blend ratios of 1,1,1,2-tetrafluoroethane and methyl chloride at -95°C. It was All polymerizations were carried out consistent with the above description. Polymerization was performed using 180 mL of diluent, 20 mL of isobutene, and 0.6 mL (2.3 mol%) of isoprene. The initiator system solution was prepared by adding 11 mL of 0.18 M HCl/CH ₂ Cl ₂ solution and 8 mL of 1.0 M hexane solution of ethylaluminum dichloride (EADC) in 80 mL of methyl chloride. For all the polymerizations of Examples 1 to 5, 5 ml of the above initiator system solution was used.

  The Raman probe was placed directly in the reaction medium to observe the progress of the reaction. The results are summarized in Table 1.

  The conversion and reaction Delta T of Examples 1 to 5 are shown in Figures 1 and 2. For methyl chloride and 1,1,1,2-tetrafluoroethane with a v/v ratio of 50/50, the highest temperature rise during the reaction, but the highest polymerization rate was observed, and the butyl rubber produced It is clear and surprising that the yield is also highest at this dilution. As shown in Figure 1, the observed temperature rise and conversion decrease as the ratio of methyl chloride or HFC-134A increases to 100%. This is an important advantage for continuous slurry manufacturing processes to maximize the throughput of the polymerization reactor.

  In addition to this, butyl rubber produced by a slurry polymerization reaction carried out in various ratios of methyl chloride and HFC-134A has a minimum of 50/50 methyl chloride and 1,1,1,2-tetrafluoroethane. Polydispersity (PDI) of. As shown in Figure 3, increasing the methyl chloride or HFC-134A results in a more polydisperse product. This is advantageous for the mixing operation to make the tire innerliner compound because the narrow molecular weight distribution can produce materials with excellent processing properties.

Claims (20)

A method for producing an elastomer, comprising at least the following steps:
a) providing a reaction medium comprising an organic diluent and at least two monomers, wherein at least one monomer is an isoolefin and at least one monomer is a multiolefin;
b) polymerizing the monomers in the reaction medium in the presence of an initiator system to produce an organic medium containing the copolymer, the organic diluent, and any residual monomers,
Where the diluent is
40 to 60% by volume of methyl chloride, and 40 to 60% by volume of 1,1,1,2-tetrafluoroethane, the two components being 90 to 100% by volume of the total volume of diluent, A method for producing an elastomer, which preferably comprises 95 to 100% by volume, more preferably 98 to 100% by volume, and even more preferably 99 to 100% by volume.   The monomers used in step a) are, based on the total weight of all the monomers used, from 80% by weight to 99.5% by weight, preferably from 85% by weight to 98.0% by weight, preferably from 85% by weight to 96.5% by weight, Even more preferably 85 wt% to 95.0 wt%, at least one isoolefin monomer, and 0.5 wt% to 20 wt%, preferably 2.0 wt% to 15 wt%, more preferably 3.5 wt% to 15 wt%. , Even more preferably from 5.0% to 15% by weight of at least one multiolefin monomer.   The method according to claim 1 or 2, wherein the isoolefin is isobutene.   The method according to any one of claims 1 to 3, wherein the isoolefin is isoprene. Diluent
42-58% by volume of methyl chloride, and 42-58% by volume of 1,1,1,2-tetrafluoroethane, the two components totaling 90 to 100% by volume of the total diluent. The method according to any one of claims 1 to 4, which comprises preferably 95 to 100% by volume, more preferably 98 to 100% by volume, even more preferably 99 to 100% by volume. Diluent
45-55% by volume of methyl chloride and 45-55% by volume of 1,1,1,2-tetrafluoroethane, said two components being in total 90-100% by volume of the total diluent 6. The method according to any one of claims 1 to 5, which comprises preferably 95 to 100% by volume, more preferably 98 to 100% by volume, even more preferably 99 to 100% by volume. Diluent
48-52% by volume methyl chloride, and 48-52% by volume 1,1,1,2-tetrafluoroethane, said two components being in total 96 to 100% by volume of the total diluent 7. The method according to any one of claims 1 to 6, which comprises preferably 98 to 100% by volume, more preferably 99 to 100% by volume, even more preferably 99.5 to 100% by volume.   8. The method according to any one of claims 1 to 7, wherein the initiator system comprises at least one Lewis acid and at least one initiator.   Lewis acid is methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum chloride, dibutyl aluminum bromide , Dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquibromide, ethylaluminum sesquibromide, ethylaluminum sesquichloride, and mixtures thereof, or including the above, preferably diethylaluminum chloride, ethylaluminum sesquichloride, ethyl Aluminum dichloride, diethyl aluminum bromide, ethyl aluminum sesquibromide), and ethyl aluminum bromide, and mixtures thereof, or a method according to claim 8.   The initiator is water, hydrogen halide, carboxylic acid, carboxylic acid halide, sulfonic acid, sulfonic acid halide, alcohol, phenol, tertiary alkyl halide, tertiary aralkyl halide, tertiary alkyl ester, Includes at least one compound selected from the group consisting of a tertiary aralkyl ester, a tertiary alkyl ether, a tertiary aralkyl ether, an alkyl halide, an aryl halide, an alkylaryl halide, and an arylalkyl acid halide. The method according to claim 8 or 9.   The method of claim 10, wherein the initiator comprises hydrogen chloride, water, and methanol.   A Lewis acid to initiator molar ratio of from 1:5 to 100:1, preferably from 5:1 to 100:1, more preferably from 8:1 to 20:1. The method described in the section.   Step b) is in the range of 20°C from the freezing point of the diluent, typically in the range of -100°C to 20°C, preferably in the range of -100°C to -50°C, even more preferably in the range of -95°C to -70. 13. The method according to any one of claims 1 to 12, carried out at a temperature in the range of °C.   Step b) is carried out in such a manner that the solids content of the slurry in step b) is in the range of 1 to 45 wt%, more preferably 3 to 40 wt%, even more preferably 15 to 40 wt%, The method according to any one of claims 1 to 13.   Step b) comprises 5% to 90%, preferably 5 to 50%, and in another embodiment 5% to 25%, preferably 10 to 20% by weight of the monomers initially used. 15. The method according to any one of claims 1 to 14, which is stopped after consumption.   16. Process according to any one of claims 1 to 15, further comprising the step c) of at least partially removing residual monomers of the monomer mixture, preferably further diluent from the reaction medium, preferably by distillation.   The elastomer is in the range of 10 to 2,000 kg/mol, preferably in the range of 20 to 1.000 kg/mol, more preferably in the range of 50 to 1,000 kg/mol, even more preferably in the range of 200 to 800 kg/mol, and even more preferably 17. The method according to any one of claims 1 to 16, having a weight average molecular weight in the range 250 to 550 kg/mol, most preferably in the range 250 to 500 kg/mol.   18. The elastomer of claim 1 wherein the elastomer has a polydispersity in the range 1.5 to 4.5, preferably 2.0 to 3.5, measured by the ratio of the weight average molecular weight to the number average molecular weight as determined by gel permeation chromatography. The method according to any one of items.   The elastomer has a Mooney viscosity of at least 30 (ML 1+8, 125° C., ASTM D 1646), preferably 30 to 60, more preferably 30 to 45 (ML 1+8, 125° C., ASTM D 1646), The method according to any one of claims 1 to 18.   An elastomer obtained according to any one of claims 1 to 19.